CN102616753A - Low-temperature mechanical alloying method for preparing sulphur selenide submicro powder material - Google Patents

Low-temperature mechanical alloying method for preparing sulphur selenide submicro powder material Download PDF

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CN102616753A
CN102616753A CN2012101072900A CN201210107290A CN102616753A CN 102616753 A CN102616753 A CN 102616753A CN 2012101072900 A CN2012101072900 A CN 2012101072900A CN 201210107290 A CN201210107290 A CN 201210107290A CN 102616753 A CN102616753 A CN 102616753A
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powder
ball
alcohol
simple substance
control agent
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CN102616753B (en
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龙飞
郑国源
池上森
莫淑一
邹正光
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Guilin University of Technology
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Guilin University of Technology
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Abstract

The invention discloses a low-temperature mechanical alloying method for preparing a sulphur selenide submicro powder material. Simple substance metal powder and simple substance non-metal powder are added into a ball mill tank and ball milled according to rated ball material ratio and set rotating speed with alcohol and amine mixing liquid serving as a process control agent, and ball mill products are washed centrifugally and dried to obtain target products. The simple substance metal powder is one of Zn powder, Sn powder and Cu powder. The simple substance non-metal powder is S powder or Se powder. The process control agent is mixture of alcohol and amine with volume ratio as 1-20:1, the alcohol is one of ethanol, glycol, n-butyl alcohol, isobutanol, isoamylol, tert-amyl alcohol and glycerol, and the amine is one of ethylenediamine, iso-butylamine, diisopropylamine, hexamethylenediamine and triethylamine. The raw material is easy to obtain, products are pure, energy consumption is low, product appearance is easy to control, technology is simple, and the method is suitable for industrial production.

Description

A kind of method of low temperature prepared by mechanical alloy sulfoselenide submicron powder material
Technical field
The present invention relates to a kind of method of low temperature prepared by mechanical alloy sulfoselenide submicron powder material, belong to the materials chemistry field, prepared material can be used for fields such as photoelectric device, thin film solar cell.
Background technology
Sulfoselenide submicron powder materials such as ZnS, ZnSe, SnSe, SnS, CuS and CuSe can be used to prepare thin film semiconductor material, electrooptical device etc.Generally; Above-mentioned materials need be that raw material could obtain through chemosynthesis with the salt through the solvent thermal synthesis method, and this speed of reaction is slow and step is miscellaneous, in the chemosynthesis process, introduces impurity easily; Therefore and be not suitable for industrial scale production yield of product is not high.
Summary of the invention
The method that the purpose of this invention is to provide a kind of low temperature prepared by mechanical alloy sulfoselenide submicron powder material.With elemental metals powder and simple substance non-metal powder is raw material, adition process control agent, control ball-to-powder weight ratio, rotational speed of ball-mill and ball milling time, low temperature prepared by mechanical alloy sulfoselenide submicron powder material.
Concrete steps are following:
(1) 1: 1 in molar ratio～1.5 take by weighing elemental metals powder and simple substance non-metal powder as raw material, take by weighing the used abrading-ball of ma process, the mass ratio of abrading-ball and raw material is 20～60: 1, measures the process control agent of volume for 0.05～0.2 times of mill tank volume;
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar together, feeding argon gas do protection gas, and jar is ground in sealing, will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 200～600 rev/mins, ball milling 5～72 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3～4 times, 70～90 ℃ of following vacuum-dryings in vacuum drying oven of the product behind the centrifuge washing were obtained target powder in 7～9 hours;
Said elemental metals powder is a kind of in Zn powder, Sn powder and the Cu powder;
Said simple substance non-metal powder is S powder or Se powder;
Said process control agent is the mixture of alcohols and amine, and the volume ratio of alcohols and amine is 1～20: 1; Said alcohols is a kind of in ethanol, terepthaloyl moietie, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, tertiary amyl alcohol and the USP Kosher, and said amine is a kind of in quadrol, isobutylamine, Diisopropylamine, hexanediamine and the triethylamine; Said absolute ethyl alcohol, terepthaloyl moietie, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, tertiary amyl alcohol, USP Kosher, quadrol, isobutylamine, Diisopropylamine, hexanediamine and triethylamine are analytical pure.
Different with the synthetic sulfoselenide submicron powder material technology of common solvent thermal, the present invention adopts low temperature mechanical alloying method to prepare target powder, has the following advantages:
(1) adopting the simple substance powder is raw material, and reaction raw materials is easy to get, and reduces cost greatly, and reaction process does not have by product, has avoided the introducing of impurity to the full extent, also helps in the building-up process the accurate control to the product stoichiometric ratio simultaneously;
(2) realize the synthetic sulfoselenide submicron powder material of low temperature, when having reduced energy consumption of reaction, can avoid product Yin Gaowen to reunite and grow up, thereby help morphology control product, the prepared little and narrowly distributing of micro-powder particle diameter is active high;
(3) technology is simple, and is easy and simple to handle, is applicable to industrial scale production.
Description of drawings
Fig. 1 is preparation technology's schema of the present invention.
Fig. 2 is the XRD diffracting spectrum of the ZnS powder of the embodiment of the invention 1 preparation.
Fig. 3 is the SEM shape appearance figure of the ZnS powder of the embodiment of the invention 1 preparation.
Fig. 4 is the sreen analysis collection of illustrative plates of the ZnS powder of the embodiment of the invention 1 preparation.
Fig. 5 is the XRD diffracting spectrum of the SnS powder of the embodiment of the invention 3 preparations.
Fig. 6 is the SEM shape appearance figure of the SnS powder of the embodiment of the invention 3 preparations.
Fig. 7 is the sreen analysis collection of illustrative plates of the SnS powder of the embodiment of the invention 3 preparations.
Fig. 8 is the XRD diffracting spectrum of the CuSe powder of the embodiment of the invention 5 preparations.
Fig. 9 is the SEM shape appearance figure of the CuSe powder of the embodiment of the invention 5 preparations.
Figure 10 is the sreen analysis collection of illustrative plates of the CuSe powder of the embodiment of the invention 5 preparations.
Embodiment
Embodiment 1: (ZnS powder)
(1) be raw material with simple substance Zn powder and simple substance S powder; Took by weighing 6.53 gram Zn powder in 1: 1 in molar ratio; 3.2 gram S powder is to take by weighing 583 at 60: 1 to restrain abrading-balls according to the mass ratio of abrading-ball and institute's raw materials weighing, measures 25mL process control agent (20mL absolute ethyl alcohol+5mL analytical pure quadrol) with graduated cylinder;
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar that volume is 500mL together, feeding argon gas do protection gas, and sealing mill jar will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 600 rev/mins, and the ball milling time is 72 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3 times, with the product behind the centrifuge washing in vacuum drying oven 80 ℃ of following vacuum-dryings 8 hours target powder, be ZnS through XRD analysis.
Embodiment 2: (ZnSe powder)
(1) be raw material with simple substance Zn powder and simple substance Se powder; Took by weighing 6.53 gram Zn powder in 1: 1.5 in molar ratio; 11.84 gram Se powder is to take by weighing 367 at 20: 1 to restrain abrading-balls according to the mass ratio of abrading-ball and institute's raw materials weighing, measures 100mL process control agent (75mL absolute ethyl alcohol+25mL analytical pure quadrol) with graduated cylinder;
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar that volume is 500mL together, feeding argon gas do protection gas, and sealing mill jar will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 600 rev/mins, and the ball milling time is 5 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3 times, with the product behind the centrifuge washing in vacuum drying oven 80 ℃ of following vacuum-dryings 8 hours target powder ZnSe.
Embodiment 3: (SnS powder)
(1) be raw material with simple substance Sn powder and simple substance S powder; Took by weighing 11.87 gram Sn powder in 1: 1.2 in molar ratio; 3.84 gram S powder is to take by weighing 628 at 40: 1 to restrain abrading-balls according to the mass ratio of abrading-ball and institute's raw materials weighing, measures 100mL process control agent (75mL absolute ethyl alcohol+25mL analytical pure quadrol) with graduated cylinder.
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar that volume is 500mL together, feeding argon gas do protection gas, and sealing mill jar will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 400 rev/mins, and the ball milling time is 12 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3 times, with the product behind the centrifuge washing in vacuum drying oven 80 ℃ of following vacuum-dryings 8 hours target powder, be SnS through XRD analysis.
Embodiment 4: (SnSe powder)
(1) be raw material with simple substance Sn powder and simple substance Se powder; Took by weighing 11.87 gram Sn powder in 1: 1 in molar ratio; 7.896 gram Se powder is to take by weighing 593 at 30: 1 to restrain abrading-balls according to the mass ratio of abrading-ball and institute's raw materials weighing, measures 50mL process control agent (25mL absolute ethyl alcohol+25mL analytical pure quadrol) with graduated cylinder;
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar that volume is 500mL together, feeding argon gas do protection gas, and sealing mill jar will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 500 rev/mins, and the ball milling time is 12 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3 times, with the product behind the centrifuge washing in vacuum drying oven 80 ℃ of following vacuum-dryings 8 hours target powder SnSe.
Embodiment 5: (CuSe powder)
(1) be raw material with simple substance Cu powder and simple substance Se powder; Took by weighing 6.4 gram Cu powder in 1: 1.5 in molar ratio; 11.84 gram Se powder is to take by weighing 547 at 30: 1 to restrain abrading-balls according to the mass ratio of abrading-ball and institute's raw materials weighing, measures 50mL process control agent (25mL absolute ethyl alcohol+25mL analytical pure quadrol) with graduated cylinder;
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar that volume is 500mL together, feeding argon gas do protection gas, and sealing mill jar will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 600 rev/mins, and the ball milling time is 5 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3 times, with the product behind the centrifuge washing in vacuum drying oven 80 ℃ of following vacuum-dryings 8 hours target powder, be CuSe through XRD analysis.
Embodiment 6:CuS powder)
(1) be raw material with simple substance Cu powder and simple substance S powder; Took by weighing 6.4 gram Cu powder in 1: 1 in molar ratio; 3.2 gram S powder is to take by weighing 480 at 50: 1 to restrain abrading-balls according to the mass ratio of abrading-ball and institute's raw materials weighing, measures 75mL process control agent (50mL absolute ethyl alcohol+25mL analytical pure quadrol) with graduated cylinder;
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar that volume is 500mL together, feeding argon gas do protection gas, and sealing mill jar will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 600 rev/mins, and the ball milling time is 24 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3 times, with the product behind the centrifuge washing in vacuum drying oven 80 ℃ of following vacuum-dryings 8 hours target powder CuS.

Claims (1)

1. the method for a low temperature prepared by mechanical alloy sulfoselenide submicron powder material is characterized in that concrete steps are:
(1) 1: 1 in molar ratio～1.5 take by weighing elemental metals powder and simple substance non-metal powder as raw material, take by weighing the long-pending used abrading-ball of tool alloying process, the mass ratio of abrading-ball and raw material is 20～60: 1, measures volume for grinding the process control agent of 0.05～0.2 times of tank volume;
(2) raw material, abrading-ball and the process control agent with step (1) weighing adds in the mill jar together, feeding argon gas do protection gas, and jar is ground in sealing, will grind jar and be transferred in the planetary ball mill, and setting rotating speed is 200～600 rev/mins, ball milling 5～72 hours;
(3) with step (2) products therefrom with zero(ppm) water and absolute ethyl alcohol centrifuge washing 3～4 times, 70～90 ℃ of following vacuum-dryings in vacuum drying oven of the product behind the centrifuge washing were obtained the target powder material in 7～9 hours;
Said elemental metals powder is a kind of in Zn powder, Sn powder and the Cu powder;
Said simple substance non-metal powder is S powder or Se powder;
Said process control agent is the mixture of alcohols and amine, and the volume ratio of alcohols and amine is 1～20: 1; Said alcohols is a kind of in ethanol, terepthaloyl moietie, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, tertiary amyl alcohol and the USP Kosher, and said amine is a kind of in quadrol, isobutylamine, Diisopropylamine, hexanediamine and the triethylamine; Said ethanol, terepthaloyl moietie, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, tertiary amyl alcohol, USP Kosher, quadrol, isobutylamine, Diisopropylamine, hexanediamine and triethylamine are analytical pure.
CN 201210107290 2012-04-11 2012-04-11 Low-temperature mechanical alloying method for preparing sulphur selenide submicro powder material Expired - Fee Related CN102616753B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475741A (en) * 2014-12-17 2015-04-01 扬州大学 Method for preparing Ti5Si3 intermetallic compound powder by mechanical alloying
CN104555951A (en) * 2014-12-31 2015-04-29 烟台佳隆纳米产业有限公司 Method for preparing and storing nano-selenium through cryogenic technology
CN104787732B (en) * 2015-03-13 2016-09-14 哈尔滨工程大学 Cobalt0.85the method for preparing solid phase of selenium compound
CN106744728A (en) * 2016-12-19 2017-05-31 陕西科技大学 A kind of method that room temperature liquid phase method prepares SnSe micron balls

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US20110065228A1 (en) * 2009-09-15 2011-03-17 Xiao-Chang Charles Li Manufacture of thin solar cells based on ink printing technology
CN102320647A (en) * 2011-08-17 2012-01-18 北京科技大学 Preparation method of copper sulphide nano-powder with different stoichiometric ratios
CN102363530A (en) * 2011-08-03 2012-02-29 北京科技大学 Preparation method of Cu1.8+xS binary thermoelectric material

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Publication number Priority date Publication date Assignee Title
US20110065228A1 (en) * 2009-09-15 2011-03-17 Xiao-Chang Charles Li Manufacture of thin solar cells based on ink printing technology
CN102363530A (en) * 2011-08-03 2012-02-29 北京科技大学 Preparation method of Cu1.8+xS binary thermoelectric material
CN102320647A (en) * 2011-08-17 2012-01-18 北京科技大学 Preparation method of copper sulphide nano-powder with different stoichiometric ratios

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GUO-LONG TAN ET AL.: "Preparation and Optical Properties of CdS Nanocrystals Prepared by a Mechanical Alloying Process", 《J. PHYS. CHEM. C》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475741A (en) * 2014-12-17 2015-04-01 扬州大学 Method for preparing Ti5Si3 intermetallic compound powder by mechanical alloying
CN104555951A (en) * 2014-12-31 2015-04-29 烟台佳隆纳米产业有限公司 Method for preparing and storing nano-selenium through cryogenic technology
CN104555951B (en) * 2014-12-31 2016-08-24 烟台佳隆纳米产业有限公司 A kind of method utilizing cryogenic technique preparation and preservation nanometer selenium
CN104787732B (en) * 2015-03-13 2016-09-14 哈尔滨工程大学 Cobalt0.85the method for preparing solid phase of selenium compound
CN106744728A (en) * 2016-12-19 2017-05-31 陕西科技大学 A kind of method that room temperature liquid phase method prepares SnSe micron balls
CN106744728B (en) * 2016-12-19 2019-03-05 陕西科技大学 A kind of method that room temperature liquid phase method prepares SnSe micron ball

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